Polymers of acryloxyacyl chlorides and use thereof

ABSTRACT

ACRYLOXYACYL CHLORIDES OF THE STRUCTURE   CH2=C(-R)-COO-ALK-CO-CL   WHEREIN R IS H OR CH3 AND ALK IS A BIVALENT HYDROCARBON RADICAL CONTAINING 1 TO 21 CARBON ATOMS. THESE COMPOUNDS MAY BE HOMOPOLYMERIZED OR COPOLYMERIZED WITH A DIFFERENT POLYMERIZABLE MONOMER (E.G., A LOWER ALKYL ACRYLATE OR METHACRYLATE). THE POLYMERS ARE USEFUL FOR APPLICATION TO FIBROUS MATERIALS, FOR EXAMPLE, TO WOOL TO MAKE IT SHRINK RESISTANT.

United States Patent US. Cl. 260-861 E 5 Claims ABSTRACT OF THEDISCLOSURE Acryloxyacyl chlorides of the structure 0 I H l]CHFC-C-O-Alk- -01 wherein -R is H or CH;, and Alk is a bivalenthydrocarbon radical containing 1 to 21 carbon atoms. These compounds maybe homopolymerized or copolymerized with a different polymerizablemonomer (e.g., a lower alkyl acrylate or methacrylate). The polymers areuseful for application to fibrous materials, for example, to wool tomake it shrink resistant.

This is a division of application Ser. No. 21,499, filed Mar. 20, 1970.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This invention relates to and has among its objects the provision of neworganic compounds, namely, acryloxyacyl chlorides, in both monomeric andpolymeric form. The objects of the invention also include methods forsynthesizing these compounds, procedures for treating fibrous materialswith the compounds, and the treated materials as new articles ofmanufacture. Further objects of the invention will be evident from thefollowing description wherein parts and percentages are by weight unlessotherwise specified.

THE MONOMERS The novel acryloxyacyl chlorides of the invention have thestructure wherein R is H or CH;,, and Alk is a bivalent aliphatichydrocarbon group, saturated or containing ethylenic unsaturation,straight chain or branched, which contains 1 to 21, preferably 9 to 21,carbon atoms.

Examples of individual compounds encompassed by the invention areprovided below by way of illustration and not limitation:

3,681,312. Patented Aug. 1, 1972 p Ce PREPARATION OF THE NEW COMPOUNDSIn the synthesis of the compounds of the invention a hydroxyaliphaticacid is reacted with acryloyl (or methacryoyl) chloride to produce thecorresponding acryloxyaliphatic (or methacryloxyaliphatic) acid. Toprevent polymerization, the reaction is carried out in the presence of asmall proportion of a polymerization inhibitor such as copper resinate,a commercial product which is an oil-soluble copper salt madeby heatingcopper sulphate with rosin oil. In a second step, the acry loxyaliphaticacid is reacted with oxalyl chloride or thionyl chloride to produce theacryloxyacyl chloride. The following formulas demonstrate the synthesisas applied, by way of example, to the preparation of 12-acryloxystearoylchloride.

no- H-(CHzho-O 0 0H lCHFCHC 0 Cl CHFCHC 0-0- H-(CHgho-C O OH C001 i :0012)s a CHpCH-C OOJ}H(CH2)10C OCL As the starting material for thesynthesis one can use various hydroxyaliphatic acids as for example:glycolic, 3- hydroxypropionic, 4-hydroxybutyric, 6-hydroxycaproic, 8-hydroxycaprylic, IO-hydroxycapric, 12-hydroxylauric, 10- hydroxycapric,12-hydroxylauric, 14-hydroxymyristic, 16- hydroxypalymitic, 9-, 10-,11-, 12-, or l8-hydroxystearic, 14-hydroxybehenic, ricinoleic,lesquerolic, and other hydroxyaliphatic acids responding to the formulaHO--Alk-COOH wherein Alk is as above defined.

PREPARATION OF POLYMERS The acryloxyacyl chlorides of the invention maybe employed to prepare useful polymers, including both homoandcopolymers. The homopolymers and copolymers are prepared by conventionalpolymerization techniques used with other acrylates and methacrylates.Typically, the polymerization is carried out in solution. Theacryloxyacyl chloride (with or without an additional co-monomer) isdissolved in an inert solvent (such as benzene, toluene, xylene, ethylacetate, dimethylformamide, etc.), a polymerization initiator is added,and the solution heated at about 50-125 0., preferably under a blanketof nitrogen, helium, or oher non-oxidizing gas. The polymerization ispreferably catalyzed by the use of an azo initiator such asazodiisobutyronitrile. Peroxide catalysts may also be used, for example,benzoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, etc. Thepolymerization products range from viscous liquids to semi-solid or evensolid materials. They are soluble in solvents such as benzene, toluene,xylene, carbon tetrachloride, etc. A critical attribute of the polymersis that they contain pendant acid chloride (-COCl) groups which provideimportant advantages as explained below.

In the processing of textiles it is often desirable to modify theproperties of the fiber, for example, to improve their shrinkagecharacteristics. Various procedures have been advocated for suchpurposes and they usually involve treatment of the textile with apolymer. A common fault of many of these procedures is that themodification has but a temporary effect as the applied substance isremoved from the fibers when they are subjected to laundering or drycleaning.

In accordance with the invention, textile materials are treated withpolymers which react with the textile materials so that the modificationachieved is deepseated and durable. In other words, the invention yieldsthe advantage that the polymer applied to the fibers is not just aphysical coating but is chemically bonded or grafted to the fibers. Thepolymers in accordance with the invention contain pendant acid chloridegroups and when the polymers are applied to the substrate, these acidchloride groups react with those radicals of the textile substrate whichhave active hydrogen atoms. Such radicals may also be termedhydrogen-donor radicals and include such types of functions as hydroxyl,primary or secondary amine, primary amide, thiol, carboxyl, etc.Virtually all fibrous materials, both natural and synthetic, contain oneor more of such types of hydrogen-donor radicals.

The polymers of the invention include not only homopolymers of theabove-described monomers, but also copolymers of the acryloxyacylchlorides with an additional monomer which does not contain an acidhalide group. Generically, the co-monomer may be any compound which iscopolymerizable with the acryloxyacyl chloride, which contains at leasta single CH ==C grouping, and which is free from a hydrogen atomreactive with an acid chloride grouping. In general, copolymers arepreferred in the treatment of textile materials because they exert aminimum stiffening eifect on the substrate. Examples of monomericsubstances which may be copolymerized with acryloxyacyl chlorides toproduce copolymers for use in practicing the invention are set forthbelow by Way of illustration but not limitation:

Alkyl esters of acrylic acid and alkyl esters of any of the variousa-alkylacrylic or a-haloacrylic acids, e.g., the methyl, ethyl, propyl,isopropyl, butyl amyl, hexyl, octyl, decyl, dodecyl, tetradecyl,hexadecyl, octadecyl, cyclohexyl, oleyl, etc., esters of acrylic,methacrylic, ethacrylic, propacrylic, chloracrylic, bromoacrylic, etc.acids.

Aryl and aralkyl esters of acrylic acid or the vz-Substituted acrylicacids, e.g., phenyl, o-, m-, p-tolyl, dodecylphenyl, benzyl,phenylethyl, etc., esters of acrylic, methacrylic, ethacrylic,propacrylic, chloroacrylic, bromoacrylic, etc, acids.

Alkyl acrylates or methacrylates containing an oxygen bridge, typicallymethoxyethyl acrylate, ethoxyethyl acrylate, propoxyethyl acrylate,butoxyethyl acrylate, octoxyethyl acrylate, cyclohexoxyethyl acrylate,benzoxethyl acrylate, phenoxyethyl acrylate, methoxyethyl methacrylate,phenoxyethyl methacrylate, etc.

Acrylates containing such radicals as thioether, sulphone, orsulphoxide, for example, the esters of acrylic acid or methacrylic acidwith alcohols of the types:

wherein R is an alkyl radical such as methyl, ethyl, propyl, butyl,etc., or an aryl or aralkyl radical such as phenyl, tolyl, benzyl,phenylethyl, etc.

4 Vinyl esters of fatty acids, e.g., vinyl acetate, propionate,butyrate, valerate, caprylate, caprate, laurate,

myristate, palmitate, stearate, oleate, etc.

Allyl and methallyl esters of fatty acids, e.g., allyl and methallylacetates, propionates, butyrates, valerates, caprylates, caprates,laurates, myristates, palmitates, stearates, oleates, etc.

N-dialkyl acrylamides and N dialkyl a substituted acrylamides, forexample, N-dimethyl, N-diethyl, N-dipropyl, N-dibutyl, N-diamyl,N-dihexyl, N-dioctyl, N- didodecyl, etc., acrylamides, methacrylamides,ethacrylamides, propacrylamides, etc.

Hydrocarbons and halogenated hydrocarbons such as styrene,u-methylstyrene, dimethylstyrenes, vinyl naphthalenes, dichlorostyrenes,vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide.

Ketones such as methyl vinyl ketone, ethyl vinyl ketone, isopropyl vinylketone and other alkyl vinyl ketones, methyl isopropenyl ketone, methylallyl ketone.

Itaconic diesters, for example, the dimethyl, diethyl, diisopropyl,dibutyl, dihexyl, didodecyl and other dial'kyl esters of itaconic acids.Diaryl and diaralkyl esters of itaconic acid, e.g., diphenyl itaconate,dibenzyl itaconate, di-(phenylethyl) itaconate, etc.

Other compounds containing the typical CH =C grouping such ascyanostyrenes, vinyl thiophene, vinyl pyridine, vinyl pyrrole,acrylonitrile, methacrylonitrile, alkyl vinyl sulphones such as ethylvinyl suphone. Compounds of the types:

ROR R1 wherein R is H or CH and wherein R is a lower alkyl group such asCH C H etc.

Although it is generally preferred to copolymerize the acryloxyacylchloride with an individual monomer such as those exemplified above, itis withinthe purview of the invention to use mixtures of two or moremonomers. Indeed, it is helpful in some instances to use a highlypolymerizable compound such as acrylonitrile in conjunction with amonomer of lesser activity such as vinyl acetate, to promote conjointcopolymerization with the acryloxyacyl chloride.

In preparing the copolymers of the invention, the proportions ofacryloxylacyl chloride and the other monomer may be varied widely. Ingeneral, one uses one mole of acryloxyacyl chloride in conjunction withabout 1 to 30 moles of the other monomer.

APPLICATION OF THE POLYMER TO THE TEXTILE The polymers of the inventionmay be applied to the textile in various ways. One technique involvesapplying the polymer as such to the textile, using heating to make thepolymer flow and distributing it with calender rolls or the like.Generally, this technique is not a preferred one because it causes astiffening of the textile and is thus suitable only in instances wheresuch stilfening effect is desirable or tolerable. A :preferred techniqueinvolves dissolving the polymer in an inert, volatile solvent andapplying the resulting solution to the textile material. Typical of thesolvents which may be used are benzene, toluene, xylene, dioxane,diisopropyl ether, dibutyl ether, butyl acetate, chlorinatedhydrocarbons such as chloroform, carbon tetrachloride, ethylenedichloride, trichloro ethylene, perchloroethylene, 1,3 dichlorobenzene,fluorohydrocarbons such as benzotrifluoride, 1,3 bis (trifluoromethyl)benzene, etc., petroleum distillates such as petroleum naphthas, etc.The concentration of the polymer in the solution is not critical and maybe varied depending on such circumstances as the solubility of thepolymer in the selected solvent, the amount of polymer to be depositedon the fibers, the viscosity of the solution, etc. In general, apractical range of concentration would be from about 1% to about 25%.The solution may be distributed on the textile material by any of theusual methods, for example, by spraying, brushing, padding, dipping etc.A preferred technique involves immersing the textile in the solution andthen passing it through squeeze rolls to remove the excess of liquid.Such techniques as blowing air through the treated textile may beemployed to reduce the amount of liquid which exists in intersticesbetween fibrous elements. In any case, the conditions of application areso adjusted that the textile material contains the proportion of polymerdesired. Usually, the amount of polymer is about from 0.5 to 20%, basedon the weight of the textile material but it is obvious that higherproportions of polymer may be used for special purposes. Preferably, intreating textile such as fabrics the amount of polymer is limited to arange of about 0.5 to 10% to attain the desired end such as shrinkresistance without interference with the hand of the textile.

After application of the polymer the treated textile is cured (heated)to effect reaction between the textile material and the polymer, thus tobond the polymer to the fibers. In cases where the polymer is applied asa dispersion-that is, a solution, emulsion, or suspension-the solvent orother volatile dispersing medium is preferably evaporated .prior to thecuring operation. Such prior evaporation is not a critical step and theevaporation may be simply effected as part of the curing step. Thetemperature applied in the curing step is not critical and usually iswithin the range from about 50 C. to about 150 C. It is obvious that thetime required for the curing will vary with such factors as thereactivity of the selected polymer, the type of textile material, andparticularly the temperature so that a lower curing temperature willrequire a longer curing time and vice versa. It will be further obviousto those skilled in the art that in any particular case the temperatureof curing should not be so high as to cause degradation of the textileor the polymer. In many cases an adequate cure is effected by heatingthe treated textile in an oven at about 100 C. for about 5 to 60minutes.

Although the present invention is of particular advantage in itsapplication to wool, this is by no means the only type of fiber whichcomes into the ambit of the invention. Generically, the invention isapplicable to the treatment of any hydrogen-donor textile material andthis material may be in any physical form, e.g., bulk fibers, filaments,yarns, threads, slivers, roving, top, webbing, cord, tapes, woven orknitted fabrics, felts or other non-woven fabrics, garments or garmentparts. Illustrative examples of hydrogen-donor textile materials are:polysaccharide-containing textiles, for instance, those formed of orcontaining cellulose or regenerated celluloses, e.g., cotton, linen,hemp, jute, ramie, sisal, cellulose acetate rayons, celluloseacetatebutyrate rayons, saponified acetate rayons, viscose rayons,cuprammonium rayons, ethyl cellulose, fibers prepared from amylose,algins, or pectins; mixtures of two or more of suchpolysaccharide-containing textiles; protein-containing textiles, forinstance, those formed of or containing wool, silk, animal hair, mohair,leather, fur, regenerated protein fibers such as those prepared fromcasein, soybeans, peanut protein, zein, gluten, egg albumin, colalgen,or keratins, such as feathers, animal hoof or horn; mixtures of any twoor more of said protein-containing textiles; mixtures ofpolysaccharide-containing textiles and protein-containing textiles,e.g., blends of wool and cotton, wool and viscose, etc.; textiles formedof or containing synthetic resins having hydroxy groups in the molecule,e.g., alkyd resins containing hydroxyl groups, polyvinyl alcohol, andpartially esterified or partially etherified polyvinyl alcohols;synthetic silk, e.g., nylon, polyurethanes, etc.; mixtures of nylon orother synthetic silk with a polysaccharide or protein fiber; mixtures ofsynthetic resins containing hydroxyl groups with nylon, polyurethanes,polysaccharide, or protein fibers. By applying the inven tion totextiles, suchv as those exemplified herein, desirable results areattained. These include: Increasing the resistance of the textile toshrinking or felting when subjected to washing operations; increasingthe resistance of the textile to becoming soiled in use; decreasing thetendency of the textile to becoming creased or wrinkled during wear orduring washing and drying operations; etc. Moreover, these desirableeffects are attained without impairing such desirable fibercharacteristics or tensile strength, abrasion resistance, porosity, andthe hand of the material so that the textiles modified in accordancewith the invention may be used in fabricating garments or otherconventional structures of any kind. The invention may be applied totextiles which contain absorbed or combined water or which have a thinfilm of water adsorbed on the surface, e.g., glass fibers, asbestos,etc. In such cases the water reacts with the polymer and insolubilizesthe latter in situ. It is within the broad compass of the invention,moreover, to apply the polymers to fibrous materials which do not havehydrogen donor groups. In such case the polymer will exist as a coatingon the fibrous elements.

EXAMPLES The invention is further demonstrated by the followingillustrative examples.

The various tests referred to in the examples were carried out asfollows:

Accelerotor Shrinkage Test: The fabric samples (5" x 6") were milled at1780 r.p.m. for 2 minutes at 40 C. in an Accelerotor with 1% sodiumoleate solution, using a liquor-to-fabric ratio of about 50 to 1. Afterthis washing operation, the samples were measured to determine theirarea and the shrinkage calculated from the original area. TheAccelerotor is described in the American Dyestuif Reporter, 45, p. 685,Sept. 10, 1956. This is a very severe test which applied to untreatedWool samples gives an area shrinkage of 4050%.

Washing Machine Shrinkage Test: The samples were washed in a reversingagitator-type household washing machine, using a 3-lb. load, watertemperature of F., and a low-sudsing detergent in a concentration of0.1% in the wash liquor. The wash cycle itself was for 75 minutesfollowed by the usual rinses and spin drying. This entire sequence wasrepeated four times. The damp material is then tumble-dried in ahousehold-type clothes drier. The dried samples were then measured andthe shrinkage calculated from the original dimensions. When untreatedsamples of wool are given a single washing by this procedure, the areashrinkage is about 30-40%.

Example 1.Preparation of l2-acryloxystearoyl chloride (A) One hundredgrams of 12-hydroxystearic acid and 1.0 gram of copper resinate weremixed at room temperature in a Pyrex glass reactor fitted with astirrer, thermometer, reflux condenser and drying tube, nitrogen inlet,dropping funnel, and heating bath. After sweeping out the system withnitrogen gas, 102 grams of acryloyl chloride was added dropwise during10 minutes, and then refluxed at 65 C. for 4 hours. The excess acryloylchloride was removed by distillation at reduced pressure to yield 149grams crude, gummy 12-acryloxystearic acid.

(B) The 149 grams of 12-acryloxystearic acid was dissolved in 250 ml. ofbenzene in the same apparatus as above and blanketing the system withnitrogen gas as before. One hundred and forty-eight grams oxalylchloride was added at room temperature during 30 minutes, and

Example 7.Preparation of various polymers A series of polymers wereprepared using the procedure described in Example 4 and varying themonomers and the ratio thereof, as tabulated below. A homopolymer ofn-butyl acrylate was also prepared for comparative purposes.

Ratio of Monomer 1 to Monomer 2 Polymer Weight Molar code No. Monomer 1Monomer 2 basis basis I n-Butyl aerylate IZ-acryloxy-stearoyl chloride5/1 14.5/1 II do do /1 2.9/1 IIL. -do 10-acryloxydecanoylchloride 5/110/1 IV do 12-acry1oxyoleoy1 chloride.. 5/1 14. 5/1 V- Methyl acrylate10-acryloxydecanoyl chlorlde 5/1 15/ 1 VI. Methyl methacrylate ..do 5/113/1 H n-Butyl acrylate None Homopolymer distillate. This wasredistilled to yield 42 grams of the de- Example 8.Treatment of fabricssired product as a clear liquid. Elemental analysis:

Theor. for C2 H37O3ClI C, 67.7% H, 10.0%; 0, 12.8%; C1, 9.5%. Found: C,65.9%; H, 9.82%; CI, 11.9%.

Example 2.Preparation of IO-acryloxydecanoyl chloride The proceduredescribed in Example 1 was applied to the following materials:

In step (A), 10 grams of IO-hydroxydecanoic acid, 14.2 g. of acryloylchloride, and 100 mg. of copper resinate were used. The crudeintermediate, l0-acryloxydecanoic acid, obtained in a yield of 17 g. wasapplied to step (B) with 50 ml. of benzene and 10 g. of oxalyl chloride.Redistillation of the crude product yielded 8.5 g. of 10-acryloxydecanoyl chloride as a clear liquid.

Example 3.-Preparation of 12-acryloxyoleoyl chloride OHFCH-Oo-O-HCH,-GH=GH(CHz)1-COG1 The procedure described in Example 1 was appliedto the following materials:

In step (A), 189 grams of ricinoleic acid and 115 grams of acryloylchloride were used. The crude intermediate, 12-acryloxyoleic acid,obtained in a yield of 207 g. was applied to step (B) with 280 ml. ofbenzene and 159 g. of oxalyl chloride. Redistillation of the crudeproduct yielded 72 g. of 12-acryloxyoleoyl chloride.

Example 4.--Copolymer of 12-acryloxystearic acid and n-butyl acrylate Asolution containing 100.0 g. n-butyl acrylate, 20.0 g.12-acryloxystearoyl chloride and 1.0 g. azobisisobutyronitrile in 500ml. toluene was heated under nitrogen atmosphere at reflux (112 C.) for2 hours. After cooling, the resulting viscous copolymer solution wasdiluted with toluene or perchloroethylene to provide 10 g. of copolymerper 100 ml. of solution. This solution was then used to treat fabrics asdescribed below.

Example 5.Homopolymer of 12-acryloxystearoy1 chloride A solution of 3 g.of l2-acryloxystearoyl chloride and 100 mg. of azobisbutyronitrile in 15ml. of benzene was refluxed for 2 hours under a blanket of nitrogen gas,yielding a viscous solution of the homopolymer in benzene.

Example 6.Copolymer of methyl acrylate and IO-acryloxydecanoyl chlorideA solution containing 10 g. of methyl acrylate, 2 g. oflO-acryloxydecanoyl chloride, and 0.1 g. of azobisbutyronitrile in 50ml. of toluene was heated under nitrogen atmosphere at reflux (112 C.)for 2 hours. After cooling, the resulting viscous solution was dilutedwith toluene or perchloroethylene to provide 10 g. of copolymer per 100ml. of solution. This solution was then used to treat fabrics asfollows.

Samples of wool fabric (6.4 oz./yd. undyed plain weave, 32 ends and 28picks per inch) were treated with solutions of the polymers diluted(with benzene or perchloroethylene) to 10% polymer concentration, usingthe following technique. A weighed fabric sample is immersed in thepolymer solution, then removed and pressed between pad rolls to removeexcess liquid, dried in air, and then cured in an oven at C. for 10minutes. The sample is then weighed to determine the polymer uptake, andthe sample is tested for shrinkage by the Accelerotor test method and/orby the washing machine test. Samples of the untreated fabric were alsosubjected to these tests. The results are tabulated below:

Area shrinkage, percent Washing machine Uptake of test (four Polymerpolymer Accelerator 76-min. applied on fabric test washes) 1 Homopolymerof butyl aerylate. The fabric treated with polymer I (the 5/1 copolymerof n-butyl acrylate and 12-acryloxystearoyl chloride) and the untreatedfabric were subjected to other tests.

' ASTM test method D-39-49, 1" wide strip.

Having thus described the invention, what is claimed is: 1. An additioncopolymer of (a) an acryloxyacyl chloride of the structure wherein R isH or CH and Alk is a bivalent aliphatic hydrocarbon radical containing 1to 21 carbon atoms, and

(b) a diflerent monomer which is polymerizable with said acryloxyacylchloride, which contains a 10 S. The copolymer of claim 1 whereinmonomer (b) is grouping, and which is free from a hydrogen atom a loweralkyl acrylate or methacrylate.

reactive with an acid chloride grouping, (c) in the proportions of aboutfrom 1 to 30 moles of monomer (b) per mole of monomer (a), Re encesCited (d) said copolymer being useful for modifying fibrous 5 UNITEDSTATES PATENTS g f ig zfi ggg g fi Z22 chemically 2,726,230 12/1955Carlson 260--86.1 R The copolymer of claim 1 wherein Alk is 3,607,8479/1971 Troussler et al. 260--486 H (CH 10 HARRY WONG, 111., PrimaryExaminer 3. The copolymer of claim 1 wherein Alk is US. Cl. XR'

s- 5s; 117 124, 126, 138.8, 140, 141, 142, 14s; H--(CH1)1o- 260-30.4,31.2, 33.2, 33.6, 33.8, 47, 63, 78.5, 79.3,

4. The copolymer of claim 1 wherein Alk is 15 79.7, 85.5 ES, 86.1 R,86.3, 86.7, 89.5 H, 486 H, 884

